KR20030048471A - Polymerisation catalyst systems and their preparation - Google Patents

Abstract

The present invention discloses a process for preparing a supported catalyst system for the production of polymers by polymerising or copolymerising one or more olefins comprising 2 to 10 carbon atoms, vinyl aromatic compounds or vinyl acetate, which process comprises the steps of providing a mesoporous support of controlled morphology and of depositing a catalyst component on the support. It further discloses the catalyst system obtained by said process and the use thereof for preparing polymers of controlled morphology.

Description

POLYMERISATION CATALYST SYSTEMS AND THEIR PREPARATION

Synthesis of inorganic mesoporous solids with a narrow and selected distribution of pore size was first achieved by Sylvania Electric Products in US-A-3,556,725.

Mobil conducted extensive research in the technical field of inorganic mesoporous solids in the 90's. This study is more specifically described in Nature, 1992, vol. 359, pp. 710-712 have led to the synthesis of the composition MCM 41 (Mobil Composition of Matter 41), which is fully disclosed in many scientific publications and patents such as, for example, US-A-5,057,296.

Currently, inorganic mesoporous oxide solids with a narrow pore size distribution of 2-10 nm are well known in the art. The solid is used as a catalyst or catalyst support and as an adsorbent. The solids are characterized by a large specific surface area with a controlled pore volume distribution, thus enabling enhanced catalytic activity or adsorption. Use of such materials as supports for polymerization catalysts is described, for example, in "Stereospecific propene polymerisation catalysis using an organometallic modified mesoporous silicate"; Tudor J. and O'Hare D., Chem. Commun., 1997, pp. 603-604.

The synthesis of silicic acid mesoporous materials is generally tetraortho silicate (TEOS), tetraalkylammonium or sodium silicate or silica precipitates are used as starting materials.

TEOS is expensive and has the disadvantage of generating ethanol during hydrolysis, but can produce mesoporous particles of several microns or less when used in neutral or acidic solutions. Another disadvantage of TEOS is its poor efficiency due to surfactant accumulation when used in neutral or acidic environments.

Cheaper silicates should be used in a base environment. This is because the silicates produce irregular shaped particles that are less than 1 micron.

In addition, the effect of pH on particle size and morphology has been studied, for example, in Di Renzo et al., Microporous and Mesoporous Materials, 1999, No. 28, pp. 437-446.

The preparation of mesoporous particles larger than 15-20 microns requires an additional binding step. Several binding methods are used, all of which have various drawbacks, including:

The extrusion method of mesoporous particles requires the use of binders, liquids and optional additives. The extrusion method is used to make elongated extrudate, but the extrudate has a variable length.

A method of agglomerating mesoporous particles with a binder, a liquid and any additives on a granulator dish is used to prepare spherical granules, but these granules have a wide size distribution.

The method of densifying mesoporous particles under pressure with a binder and optionally a liquid is used to produce particles of several mm or more for pharmaceutical use.

Spray drying methods are used to produce particles of 20 to 200 microns with a narrow particle size distribution, but have poor mechanical properties when no binder is used.

Thus, both of these methods require the use of a substantial percentage of binder to produce the shaped catalyst. Therefore, there is a need for a method of producing 1 micron to several millimeters of mesoporous particles in a controlled form that can avoid these drawbacks.

It is particularly important to control the size and shape of the particles in the art of olefin polymerization, in which it is known that the shape of the final polymer is determined by the size and shape of the catalyst particles and the size and shape of the support. This is known as "replication phenomenon", and is well known in the art of ethylene polymerization using, for example, chromium catalysts. Examples of catalysts based on mesoporous supports are already described in the literature, but these catalysts are still difficult to use small particles with poor fluidization because the carrier particles do not have morphological control. Thus, the use of such particles results in poor fluff morphology, as described, for example, in Ki-Soo Lee et al., Journal of Molecular catalysis A: Chemical, 159, 301-308, 2000.

The present invention relates to the use of special mesoporous inorganic oxide supports for preparing catalyst systems suitable for preparing polymers in controlled forms.

It is an object of the present invention to produce a polymerization catalyst system using a controlled form of mesoporous support obtained without using a densification step.

It is also an object of the present invention to produce a polymerization catalyst system having a controlled pore size distribution consisting of a network of defined diameter mesoporous pores and a defined microporous percentage.

It is a further object of the present invention to produce polymers in controlled form using such catalyst systems.

It is a further object of the present invention to produce polymers that are essentially free of fine powders using such catalyst systems.

The present invention

(a) providing a mesoporous support in a controlled form,

(b) depositing a catalyst component on the support of step (a)

A method of preparing a supported catalyst for preparing a polymer by polymerizing or copolymerizing one or more olefins, vinyl aromatic compounds or vinyl acetates having 2 to 10 carbon atoms, including

The mesoporous support consists of first and / or second inorganic mesoporous particles having a size of at least 2 microns, D10 and at least 10 microns, with a size of 10 mm or less, preferably 3 mm or less, more preferably 1.5 mm or less. It is represented by the formula M _{n / q} (W _a X _b Y _c Z _d O _h ),

In the above formula,

M represents at least one ion selected from the group consisting of ammonium, IA, IIA and VIIB, for example hydrogen ions and / or sodium ions,

n and q represent the equivalent fraction and valence of M ion (s), respectively, and n / q represents the mole number or mole fraction of M ion (s),

W represents at least one divalent element such as manganese, cobalt, iron and / or magnesium,

X represents at least one trivalent element such as aluminum, boron, iron and / or gallium,

Y represents at least one tetravalent element such as silicon, titanium and / or germanium, preferably silicon,

Z represents one or more pentavalent elements such as phosphorus,

O represents oxygen,

a, b, c and d represent the mole fractions of W, X, Y and Z, respectively, a + b + c + d = 1,

1 ≤ h ≤ 2.5,

The microporous volume (pore size of 2 μm or less) is 10% or less of the total porosity volume of 300 nm or less,

For pore sizes of 2 to 10 nm, the mesoporous volume is at least 0.18 cm ³ / g, preferably at least 0.3 cm ³ / g, and the maximum peak diameter (Dmax) of the DFT distribution is 2 ≦ Dmax ≦ 5 nm A pore volume associated with a pore size of Dmax ± 15% represents at least 70%, preferably at least 80%, most preferably at least 90% of the pore volume associated with a pore size of 2-10 nm, or

For pore sizes of 4 to 15 nm, the mesoporous volume is at least 0.70 cm ³ / g, preferably at least 1 cm ³ / g, and the maximum peak diameter (Dmax) of the DFT distribution is broadly comprised of 4 to 15 nm. The pore volume associated with the pore size of Dmax ± 20% is characterized by representing at least 45%, preferably at least 50% and most preferably at least 90% of the pore volume associated with a pore size of 4-15 nm.

It is preferred that the polymers prepared according to the invention have a controlled form.

D10, D50 and D90 are defined as the maximum particle diameters respectively associated with 10%, 50% and 90% by weight of the particles.

It is preferable that it is 5 microns or more, and, as for D10, it is more preferable that it is 10 microns or more. It is preferable that D50 is 20-150 microns.

The method for producing mesoporous particles used in the present invention

(a) optionally in the presence of a soluble swelling agent, preferably trimethylbenzene in micelles

(1) a first and / or second particle having a D10 of at least 2 microns and a D50 of at least 10 microns, with a size of 10 mm or less, formula M _{n / q} (W _a X _b Y _c Z _d O _h ) (Wherein M, W, X, Y, Z, O, n, q, a, b, c, d and h have the same meaning as described above), and the particle shape and particle size of the silica source A solid inorganic source whose distribution is close to that of the support,

(2) agents capable of moving said solid inorganic source,

(3) preparations that can correct pores, such as surfactants,

(4) solvent, preferably water

Contacting and reacting

(b) filtration, washing, drying, and finally removing the calibrating agent and substantially modifying the size and shape of the starting particles as observed by scanning electron micrographs (SEM) and laser granulation measurement systems. Calcination of the inorganic particles obtained in step (a) under conditions of temperature, stirring and duration of

It includes.

Porous volume is measured by N ₂ adsorption at 77 ^° K.

The relative pore volume for pore sizes from 2 to 300 nm is measured by the DFT method (cylindrical pore). The relative porous volume (microporous volume according to IUPAC) for pore sizes up to 2 nm is measured by t-plot method.

Structural porous volume is defined as the pore volume associated with pores having a diameter below the median diameter increased up to 5 nm. The tissue porous volume is defined as the pore volume associated with pores with a diameter above the median diameter increased up to 5 nm. The pore volume distribution is measured by the DFT used in the case of cylindrical pores.

The calibrator used in the present invention may be a surfactant containing quaternary ammonium or phosphonium substituted by aryl or alkyl having 6 to 36 carbon atoms, said substituents being associated with hydroxide anions, halides or silicates And may be the same or different. For example, the correcting agent may be an ion such as cetyltrimethylammonium, cetyltrimethylphosphonium, octadecyltrimethylammonium, octadecyltrimethylphosphonium, benzyltrimethylammonium, cetylpyridinium, decyltrimethylammonium, dimethyldidodecylammonium, trimethyldode As well as amines such as dodecylamine and hexadecylamine.

The solvent may be an organic solvent and is preferably water.

The oxide transfer agent may be an inorganic base or an organic base, and is preferably soda.

The pH of the reaction mixture is generally not critical but can vary from 1 to 14. Crystallization can be carried out under unstirred or moderate agitation to avoid particle friction. The crystallization temperature is from room temperature to 200 ° C., and the reaction time is from several minutes to several days or less.

The reaction time can be optimized by SEM and laser granulation measurement system control. Too long reaction times can produce degraded particles or increase the production of fine powder.

The reaction product formed is suspended in a solvent, the suspension is filtered, washed and dried and further calcined to remove the surfactant. The final product is a solid inorganic particle with homogeneous pore size of cubic or hexagonal symmetry. The pores with hexagonal symmetry are parallel to each other.

The starting inorganic solid according to the invention is preferably of the formula M _{n / q} (X _b Y _c O _h ). Wherein X is Al, Y may be Si or Ti or a mixture thereof, b + c = 1, b ≦ 1, and Y is Si.

According to the invention, the solid form of mesoporous particles in controlled form is a chromium-based catalyst system or a metallocene catalyst system for producing a polymer in controlled form, or a Ziegler-Natta catalyst system or a late transition metal. metal) is used as a support for producing the catalyst system.

The catalyst system may be a supported chromium-based catalyst in which chromium is deposited on the support by any method known in the art. The process for preparing the chromium-based catalyst comprises the steps of providing the mesoporous catalyst support of the present invention and on the support a chromium compound, preferably chromium (III) acetylacetonate, chromium (III) acetate, chromium (III) oxalate and Depositing a chromium salt compound selected from one or more of chromium (III) stearate. Alternatively, the chromium compound may be chromosene, other organic chromium complexes or CrO ₃ or derivatives thereof. The catalyst composition comprises 0.4 to 4% by weight of chromium, based on the weight of the chromium-based catalyst.

Optionally, the support may be further modified by treatment with one or more compounds selected from the group consisting of Al, P, B, Ti and Mg, which treatment may be performed before, during or after chromium deposition. For example, the support can be treated with an aluminum compound to form an alumina containing silica support, after which the alumina containing support is impregnated with chromium by treatment with a chromium salt. In another embodiment, the support is treated with a chromium salt to impregnate chromium on the support, and the chromium impregnated support is then treated with an aluminum alkyl compound to incorporate alumina into the support. The support may comprise 0.5 to 4% by weight of aluminum based on the weight of the chromium-based catalyst. The aluminum compound may be one or more aluminum alkyl compounds such as triisobutyl aluminum (TIBAL), triethyl aluminum (TEAL), tri-n-hexyl aluminum (TNHAL), tri-n-octyl aluminum (TNOAL) or methyl aluminum oxane ( MAO) or one aluminum alcoholate, such as aluminum sec-butoxide.

Alternatively, the support is treated with a titanium compound such as titanium tetraisopropoxide to form a titanated and supported chromium-based catalyst having a titanium content of 1-5 wt% based on the weight of the titanated chromium-based catalyst. You can.

Finally, chromium may be introduced into the initial silica source prior to transformation into mesoporous materials.

The catalyst component deposited on the support may be any metallocene catalyst known in the art for the polymerization of olefins. Such catalysts are described, for example, in EP-A-0,790,259.

The catalyst can be represented by the following formulas (I), (II) and (III):

Formula I

(CpR ' _k ) _m Y _2-m MR " _n X _q

Wherein Cp is a substituted or unsubstituted cyclopentadienyl ring and each R 'is the same or different and is a hydrogen or a hydrocarbyl radical containing 1 to 20 carbon atoms, such as alkyl, An alkenyl, aryl, alkylaryl or arylalkyl radical, or two carbon atoms connected together to form a C ₄ to C ₆ ring, Y is a Group Va or Group VIa element, M is a Group IVb, Group Vb, or VIb Is a group transition metal, R ″ is a C ₁ to C ₄ alkylene radical, dialkyl germanium or silicon or siloxane bridging two (C ₅ R ′ _k ) rings or one (C ₅ R ′ _k ) ring, or Alkyl phosphine or amine radical, heteroatoms Y, X are halogen, m is 1 or 2, n is 0 to 3, q is 0 to 3, and the sum of m + n + q is the oxidation state of the metal Is the same as

Formula II

(C ₅ R ' _k ) _g R " _s (C ₅ R' _k ) MQ _3-g

Formula III

R " _s (C ₅ R ' _k ) ₂ MQ'

Wherein (C ₅ R ′ _k ) is cyclopentadienyl or substituted cyclopentadienyl, each R ′ is the same or different and is hydrogen or a hydro containing 1 to 20 carbon atoms Carbyl radicals such as alkyl, alkenyl, aryl, alkylaryl or arylalkyl radicals, or two carbon atoms are joined together to form a C ₄ to C ₆ ring, where R "is two (C ₅ R ' _k ) C ₁ to C ₄ alkylene radicals, dialkyl germanium or silicon or siloxanes, or alkyl phosphine or amine radicals that bridge the ring, Q is a hydrocarbonyl radical having 1 to 20 carbon atoms, such as aryl, alkyl , Alkenyl, alkylaryl or arylalkyl radical, hydrocarboxy radical having 1 to 20 carbon atoms or halogen, may be the same or different from each other, Q 'having 1 to about 20 carbon atoms An alkylidene radical, s is 0 or 1, g is 0, 1 or 2, s is 0 when g is 0, k is 4 when s is 1, k is 5 when s is 0, and , M is as defined above.

Examples of hydrocarbyl radicals are methyl, ethyl, propyl, butyl, aryl, isoamyl, hexyl, isobutyl, heptyl, octyl, nonyl, decyl, cetyl, 2-ethylhexyl, phenyl and the like. Examples of halogen atoms include chlorine, bromine, fluorine and iodine, with chlorine being preferred among these halogen atoms.

Examples of hydrocarboxy radicals include methoxy, ethoxy, propoxy, butoxy, amyloxy and the like.

Examples of alkylidene radicals are methylidene, ethylidene and propylidene and i-butylidene.

The active site should be formed by adding a promoter having an ionizing action such as a boron or fluorine containing compound such as a tetrakis (pentafluorophenyl) borate compound.

Alumoxane can also be used as a promoter. When alumoxane is used as a promoter, any alumoxane known in the art can be used in the present invention.

Preferred alumoxanes include oligomeric linear and / or cyclic alkyl alumoxanes represented by the following formulas IV and V:

Formula IV

Oligomeric Linear Alumoxanes

Formula V

Oligomeric Cyclic Alumoxanes

And In the formula, n is 1 to 40, preferably 10 ~ 20, m is 3 to 40, preferably 3 ~ 20, R is C ₁ ~ C ₈ alkyl group, preferably methyl.

The catalyst system may be a supported Ziegler-Natta catalyst system prepared according to any method known in the art. The Ziegler-Natta catalyst system consists of a transition metal component (A), an organoaluminum component (B) and optionally an internal electron donor (C) deposited on the mesoporous support of the invention.

The transition metal compound (A) is a reaction product of an organomagnesium compound or magnesium halide with a transition metal halide. The transition metal is selected from the group consisting of titanium, vanadium and zirconium, or a combination thereof. The transition metal is preferably titanium. Suitable titanium compounds for the preparation of component A are tetravalent halogenated titanium compounds, preferably titanium compounds of the formula TiX _n (OR) _4-n , wherein n is 1 to 4 and X represents chlorine or bromine It is preferred that X is chlorine, and R represents the same or different hydrocarbon radicals, in particular straight or branched chain alkyl groups having 1 to 18 carbons, preferably 1 to 10 carbon atoms.

The organoaluminum compounds used are reaction products of aluminum trialkyl or aluminum dialkyl hydrides with hydrocarbon radicals having 1 to 16 carbon atoms, preferably Al (iBu) ₃ or Al (iBu) ₂ H and 4 Diolefins containing from 20 to 20 carbon atoms, preferably isoprene. For example, the organoaluminum compound is aluminum isoprenyl.

The internal electron donor can be selected from the group consisting of phthalates, 1,3-diethers and tetrahydrofuran (THF).

The catalyst system may be a supported back transition metal catalyst system in which the back transition metal is deposited on the mesoporous support of the present invention by any method known in the art. The method is similar to the method used in the case of supported metallocene catalysts. The active site is formed by adding a promoter having an ionizing action such as alumoxane.

The present invention also provides a catalyst system for the production of controlled form polyolefins.

All of the catalyst systems described above are supported on mesoporous supports having mesopores concentrated at diameters of 7 nm or more.

The invention also provides a process for polymerizing one or more vinyl containing monomers, including olefins, vinyl aromatic compounds or vinyl acetates comprising 2 to 10 carbon atoms in the presence of a supported catalyst system. The olefin is preferably ethylene or propylene. The polymer thus obtained has a form which is determined by the form of the catalyst supported on the mesoporous support of the invention and thus can be controlled and is substantially free of fine powder.

The polymerization process may be performed by any one of a gas phase polymerization process, a liquid phase polymerization process, a slurry polymerization process, or a slurry bath polymerization process.

Example 1

Preparation of Support S1 According to the Invention

(1) In an 8 cm diameter 1 l cylindrical reactor, a solution of 310 ml of water, 8.3 g of soda and NORANIUM® MS 50 29.4 g was prepared. NORANIUM® MS 50 is sold by CECA and is a trimethylalkylammonium chloride containing an alkyl chain having a length of 16 to 18 carbon atoms.

(2) 33 g of a commercially available (anhydrous equivalent) silica sold under RHODIA under the name ZEOSIL® 175 MP under stirring (paddle or anchor stirrer) at room temperature. The silica has a wide pore size distribution concentrated at about 20 nm. Its granulation measurement system shows a major peak at about 150 microns, is characterized by the presence of a wide end distribution for fine particles and no particles below 4 microns at all.

(3) Under continuous stirring, the temperature was raised to 100 ° C. and maintained at 100 ° C. for 3 hours in a double sealed reactor maintained at a constant temperature by an oil bath. The solid was then filtered under vacuum on a burner filter and washed with 6 l of demineralized water. It was dried overnight in a ventilated stove at 90 ° C., raised from room temperature (25 ° C.) to 550 ° C. in 5 hours, and calcined at 550 ° C. while maintaining at 550 ° C. for 2 hours.

(4) The final solids are characterized by N ₂ adsorption / desorption (ASAP 2010, MICROMERITICS) at 77 ° K and by laser granulation measurement system (MALVERN). Pore size distribution is calculated by the DFT method. The properties of the final product are summarized in Table 1 below.

S1 Surface BETm ² / g Structural Porous Volume (2-10 nm) cm ³ / g Medium pore diameter Medium particle diameter μm Final inorganic solids 1126 0.8 3.1 90

In addition, the granulation measurement system of the final solids is characterized by the presence of a wide end distribution for the fine powder, as in the starting material, and no particles of less than 4 microns. Therefore, the granulation measurement system of the starting silica was continued, where the distribution of the starting solid and the final solid were not identical but very similar. In the process of the present invention, no fine powder was produced (particles of 4 microns or less were present at 0%) and the form of starting material was maintained.

Example 2

Preparation of Support S2 According to the Invention

These large pore mesoporous materials were prepared as follows:

(1) A solution of 620 ml of water, 16.6 g of soda and 58.8 g of NORANIUM® MS 50 was prepared.

(2) 52 g of 1,3,5-trimethylbenzene (TMB) was added under stirring to dissolve the molecules into the surfactant micelles.

(3) After 15 minutes of constant stirring, 66.14 g of SILOPOL 2104 (anhydrous equivalent) was added to the mixture under slow stirring. SILOPOL 2104 is commercially available from GRACE. The SILOPOL 2104 has a wide pore size distribution concentrated at 0% of particles below 15 microns and about 20-40 nm.

(4) The temperature was raised to 100 ° C. under stirring and maintained at 100 ° C. for 16 hours.

(5) The solid formed was filtered and washed with 3 1 water. It was dried in a ventilated stove at 70 ° C. and the temperature was raised from 25 ° C. to 550 ° C. in 5 hours and calcined at 550 ° C. while maintaining the temperature at 550 ° C. for 2 hours.

The starting solids and the final solids are characterized using the same method as in support S1, the results of which are summarized in Table 2 below.

S2 Surface BETm ² / g Structural porous volume (4 ~ 15 nm) cm ³ / g Histological porous volume (15 ~ 300 nm) cm ³ / g Maximum peak nm in diameter of the DFT distribution D10 μm D50㎛ Departure Silica 324 0.20 1.53 20-40 30 46 Final Weapon Solid 1070 1.70 0.11 9 8.2 46

The granulation measurement system of the final solids was very similar to that of the starting material as can be seen from D50.

Example 3

Preparation of Supported Chromium-Based Catalyst CR1 Using Support S1

Supported chromium-based catalysts were prepared using the support S1 of Example 1 and described in Chem. Eur. J., No. 16, 6, 2000, p. 2960-2970. The chromium acetyl acetonate [Cr (acac) ₃ ] complex was grafted onto the surface of the support S1.

Activation was then performed in a quartz tube activator under fluidization. The catalyst was heated and maintained at a temperature of 600 ° C. for 6 hours under a 200 NI / h dry air stream. While cooling to room temperature, when the temperature reached 400 ° C., the air was replaced with anhydrous nitrogen. To prevent contamination, the activated catalyst was stored under dry nitrogen.

Example 4

Preparation of Supported Chromium-Based Catalysts CR2 Using Support S2

The supported chromium-based catalyst was prepared exactly as described in Example 3 using the support S2.

Example 5

Two supported chromium-based catalysts CR1 and CR2 were used to homopolymerize ethylene.

Polymerization conditions and results are summarized in Table 3 below.

Temperature Activation g / g / h M12g / 10 ' HLMIg / 10 ' CR1 102 591 n.a. 0.77 106 694 n.a. 1.54 110 639 0.039 4.1 CR2 106 1277 n.a. 7.21 106 580 n.a. 4.86 108 1190 0.1 12.1 n.a. means too low to be valid.

MI2 and HLMI were measured by performing the method of standard test ASTM-D-1238 under respective loads of 2.16 kg and 21.6 kg at a temperature of 190 ° C.

Catalysts based on large pore mesoporous material S2 are observed to have higher activity than catalysts based on S1 mesoporous support. Mesoporous supports with pore sizes greater than 7 nm tend to produce catalysts with high activity.

Comparative Example 1

Supported Chromium-Based Polymerization Catalyst Based on MCM-41 Support

Two chromium-based catalysts are prepared using MCM-41 mesoporous silica support and described in Chem. Eur. J., No. 16, 6, 2000, p. 2960-2970. Chromium acetyl acetonate [Cr (acac) ₃ ] complexes were deposited on the surfaces of two mesoporous crystalline materials, namely Al containing silica support (CR3) with a Si / Al molar ratio of 27 and pure silica support (CR4). The catalyst thus obtained had a poor form and had to be milled to a size of 350 to 500 microns after pelletizing.

Activation was then performed in a quartz tube activator. The catalyst was heated and maintained at a temperature of 650 ° C. for 6 hours with a dry air flow of 200 NI / h. While cooling to room temperature, when the temperature reached 400 ° C., the air was replaced with anhydrous nitrogen. The activated catalyst was yellow and stored under dry nitrogen to avoid contamination.

The polymerization was carried out in a 4 liter stainless steel autoclave. The catalyst was introduced into a transparent anhydrous vessel under nitrogen flow. The reactor was closed and 2 l of isobutane were introduced into the vessel. The system was heated at 104 ° C. under stirring and then ethylene was introduced into the system. The total pressure was maintained at 31.4 bar to dissolve about 6% by weight of ethylene in isobutane. During the polymerization reaction, ethylene was added to the system to maintain the total pressure at a constant value of 31.4 bar. Continuous stirring at 450 rpm was maintained for the duration of the reaction to ensure homogeneity of the system and sufficient ethylene dissolution.

The results are summarized in Table 4 below.

catalyst CR3 CR4 Active g / g / h 140 63 MI2 g / 10 ' Too low Too low MI5 g / 10 ' 0.004 0.028 HLMI g / 10 ' 0.564 1.381 SR5 141 49 Bulk Density g / cm ³ 0.201 0.201

MI5 was measured by performing the method of standard test ASTM-D-1238 under a load of 5 kg at a temperature of 190 ° C. SR5 is defined as the ratio of HLMI / MI5.

Bulk density is standard test U.O.P. It was measured by following the method of 294-88.

As can be seen, the polymerizations carried out using the supported chromium-based catalysts of the present invention had much higher activity than prior art catalyst systems. While not wishing to be bound by any particular theory, it is believed that the superior form of the catalyst system of the present invention induces better fluidization during activation of the catalyst and therefore leads to higher activity. In addition, in the present invention, the second pores not only generate excellent diffusion of the reactants but also generate excellent activity.

Due to the better particle morphology, the fluff morphology is at least comparable to that obtained by standard silica catalysts, and much better than that obtained with normal mesoporous MCM-type materials.

Example 6

Preparation of Supported Metallocene Catalyst System M1 Based on Support S1

6.05 g of dried mesoporous support S1 was suspended in 100 ml of toluene to form a yellow suspension. 15.5 ml of a 30% by weight solution of methylalumoxane (MAO) was added dropwise to the suspension, which was reacted for 4 hours under stirring and reflux of nitrogen. The suspension was filtered and no MAO was found in the mother liquor. The precipitate was washed twice with 50 ml of toluene and three times with pentane to facilitate the drying step. The solid was then dried overnight under moderate pressure of 20 mbar. 11.22 g of a white free flowing powder were obtained.

5.01 g of the support reacted with MAO were suspended in 100 ml of toluene. 0.203 g of tetrahydroindenyl zirconium dichloride was poured into the suspension, which turned orange. The reaction was run for 2 hours. The reaction was then filtered to give a colorless filtrate, which resulted in a good fixation of the total amount of metallocene on the support. The precipitate was washed twice with 50 ml of toluene and three times with pentane. It was then dried for about 2 hours under a medium vacuum of 20 mbar. 5.03 g of pale yellow powder was isolated.

Example 7

Metallocene catalyst system M1 was used to copolymerize ethylene and hexene comonomers under and without hydrogen. Polymerization conditions and results are summarized in Table 5 below.

Comparative Example 2

The supported metallocene catalyst M2 was prepared by following the method of Example 6, except that the support was standard silica having a pore volume of 1.6 cm ³ / g and specific surface area of 300 m ² / g, and tetrahydroindenyl 0.203 The exception is that g is used instead of 0.3 g. The catalyst was used to copolymerize ethylene with hexene comonomers under and without hydrogen. Polymerization conditions and results are summarized in Table 5 below.

catalyst M1 hydrogen NI M2 hydrogen ni 0 0.5 0 0.5 Hexene weight% 1.83 1.83 1.83 1.83 Yield g 214.9 615 478.5 510.7 Productivity g / g 7192 8772 6372 6705 Active g / g / h 7192 8772 6372 6705 MI2 g / 10 ' Too low 0.006 Too low Too low HLMI g / 10 ' 0.416 0.977 0.788 2.024 Bulk Density g / cm ³ 0.297 0.222 0.254 0.291 <<< weight% 0.0 0.2 0.0 0.0 63 micron weight percent 0.2 1.2 0.2 0.0 125 micron weight percent 1.4 3.2 1.8 1.6 250 micron weight percent 9.5 7.4 8.5 12.0 500 micron weight% 48.9 28.8 30.0 40.4 1000 micron weight% 33.6 43.7 28.4 35.9 1600 micron weight percent 3.0 10.7 8.9 4.4 2000 micron weight percent 3.4 4.8 22.2 5.6

As can be seen in Table 5 above, the activity of the catalyst system according to the present invention is 50% higher in the amount of metallocene in the comparative example but much higher than the activity of the catalyst system of the prior art.

Claims (22)

(a) providing a mesoporous support in a controlled form, (b) depositing a catalyst component on the support of step (a) A process for preparing a supported catalyst for preparing a polymer by polymerizing or copolymerizing one or more olefins, vinyl aromatic compounds or vinyl acetates having 2 to 10 carbon atoms, including The mesoporous support consists of inorganic mesoporous particles having a D10 of at least 2 microns and a D50 of at least 10 microns, represented by the formula M _{n / q} (W _a X _b Y _c Z _d O _h ), In the above formula, M represents at least one ion selected from the group consisting of ammonium, IA, IIA and VIIB, n and q represent the equivalent fraction and valence of M ion (s), respectively, and n / q represents the mole number or mole fraction of M ion (s), W represents at least one divalent element, X represents one or more trivalent elements, Y represents at least one tetravalent element, Z represents one or more pentavalent elements, O represents oxygen, a, b, c and d represent the mole fractions of W, X, Y and Z, respectively, a + b + c + d = 1, 1 ≤ h ≤ 2.5, The microporous volume (pore size of 2 μm or less) is 10% or less of the total porosity volume of 300 nm or less, For pore sizes of 2 to 10 nm, the mesoporous volume is at least 0.18 cm ³ / g, preferably at least 0.3 cm ³ / g, and the maximum peak diameter (Dmax) of the DFT distribution is 2 ≦ Dmax ≦ 10 nm, preferably Preferably the pore volume associated with a pore size of 2 ≦ Dmax ≦ 5 nm and a pore size of Dmax ± 15% is at least 70%, preferably at least 80% and most preferably 90 of the pore volume associated with a pore size of 2-10 nm. Represents at least%, or For pore sizes of 4 to 15 nm, the mesoporous volume is at least 0.70 cm ³ / g, preferably at least 1 cm ³ / g, and the maximum peak diameter (Dmax) of the DFT distribution is broadly comprised of 4 to 15 nm. , Porosity volume associated with a pore size of Dmax ± 20% represents at least 45%, preferably at least 50%, most preferably at least 90% of the pore volume associated with a pore size of 4-15 nm. . The method of claim 1, wherein the polymer is in a controlled form. The method of claim 1 or 2, wherein the mesoporous volume is at least 0.3 cm ³ / g. The method according to claim 1, wherein M is hydrogen ions and / or sodium ions. 5. The method of claim 1, wherein W is manganese, cobalt, iron and / or magnesium. The method according to claim 1, wherein X is aluminum, boron, iron and / or gallium. The method of claim 1, wherein Y is silicon, titanium and / or germanium. 8. The method of any one of claims 1 to 7, wherein Z is phosphorous. The starting inorganic solid of claim 1, wherein the starting inorganic solid has the formula M _{n / q} (X _b Y _c O _h ), wherein X is Al and Y is Si or Ti, or A mixture wherein b + c = 1 and b ≦ 1. The method of claim 8, wherein Y is Si. The method of claim 1, wherein D 10 is at least 5 microns. The method of claim 1, wherein the D 50 is 20-150 microns. The method of claim 1, wherein the fine powder is 0% produced. A chromium-based catalyst system supported on a mesoporous inorganic oxide support in a controlled form according to any one of claims 1 to 13. Metallocene catalyst system supported on a mesoporous inorganic oxide support in a controlled form according to any one of claims 1 to 13. A Ziegler-Natta catalyst system supported on a mesoporous inorganic oxide support in a controlled form according to any one of claims 1 to 13. 14. A back transition metal catalyst system supported on a mesoporous inorganic oxide support in a controlled form according to any one of claims 1 to 13. 18. The supported catalyst system of claim 14, wherein the mesoporous diameter is concentrated at a diameter of at least about 7 nm. A supported chromium-based catalyst system wherein chromium is introduced into an initial silica source before it is transformed into a mesoporous material. 20. The supported chromium-based catalyst system of claim 19 wherein the mesopore diameter is concentrated at a diameter of at least about 7 nm. 21. A process for polymerizing or copolymerizing at least one olefin, vinyl aromatic compound or vinyl acetate comprising 2 to 10 carbon atoms in the presence of the supported catalyst system of any one of claims 14-20. The method of claim 21 wherein the olefin is ethylene or propylene.